United States
Environmental Protection
Agency
Environmental Monitoring
Systems Laboratory
P.O. Box 93478
Las Vegas NV 89193-93478
Pre-issue Copy
October 1987
Research and Development
An Interlaboratory Study
of Inductively Coupled
Plasma Atomic Emission
Spectroscopy Method 6010
and Digestion Method 3050

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                                 PROJECT SUMMARY
             AN INTERLABORATORY STUDY OF INDUCTIVELY COUPLED PLASMA
                    ATOMIC EMISSION SPECTROSCOPY METHOD 6010
                            AND DIGESTION METHOD 3050

                                        by

            Clifton L. Jones, Vernon F. Hodge, Donald M. Schoengold,
            Homigol Biesiada, Thomas H. Starks, and Joseph E. Campana
                          Environmental Research Center
                          University of Nevada, Las Vegas
                           Las Vegas, Nevada 89119-9770
                            Contract Number 68-01-7159
                            Contract Number 68-01-7253
                                Technical Monitor

                                Thomas A. Hinners
               Quality Assurance and Methods Development Division
                      U.S. Environmental Protection Agency
                          Las Vegas, Nevada 89193-3478
X
                   ENVIRONMENTAL MONITORING SYSTEMS LABORATORY
(v,                     OFFICE OF RESEARCH AND DEVELOPMENT
Ği                    U.S. ENVIRONMENTAL PROTECTION AGENCY
x                        LAS VEGAS, NEVADA 89193-3478
O
^                                  MAY 1987
o

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                           NOTICE








     The information in this  document has been funded wholly or



in part by  the  United States  Environmental Protection Agency



under Contract Number  68-01-7159 to the University of Nevada,



Las Vegas,  Nevada, and under Contract Number 68-01-7253  to Viar



and Company, Alexandria,  Virginia.  It has been subject to the



Agency's peer  and administrative  review,  and it has  been



approved for publication as an EPA document.
                              11

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                          ABSTRACT







     The design, execution,  and results of an interlaboratory



study of Method  6010,  "Inductively Coupled Plasma  Atomic



Emission Spectroscopy," are described.   This study examined the



application of  the  method to  the analysis  of solid-waste



materials for 23 elements.   Part  of  the interlaboratory  study



included a study of Method  3050, "Acid  Digestion of Sediments,



Sludges and Soils," which  is integral  to Method 6010 when



considering the analysis of certain solid wastes.  The overall



study was designed  so that the variability of the two  methods



was separable.   Method performance data,  including precision



and accuracy, are presented and discussed.  A comparison of the



inductively coupled plasma atomic  emission  and  atomic



absorption spectroscopic  techniques is  presented, as well as a



comparison of results from  two different types of inductively



coupled plasma  spectrometers.   The limitations of the  methods



are described, and suggestions are given  to improve the general



application of Method 6010.
                            iii

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                      ACKNOWLEDGMENTS
     Use of  the EPA  contracts numbered 68-01-7159 and



68-01-7253 for this study was  graciously  permitted by the



respective project officers,  Duane A.  Geuder  and Michael  H.



Carter.
                            IV

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                        INTRODUCTION
     An interlaboratory  study of solid wastes using the EPA



analytical Method 6010 entitled  "Inductively Coupled Plasma



Atomic Emission Spectroscopy" (ICP-AES), which is included  in



the EPA methods publication  SW-846,  was performed with nine



participating laboratories.  This  inter laboratory  study



concentrated on  the application of  Method 6010 for  the



determination of 23  elements in seven solid  materials including



dried sludges, sediments,  and fly ash.   The 23 target elements



are:  Al, Sb, As, Ba, Be,  Cd, Ca,  Cr, Co,  Cu, Fe, K, Pb, Mg,



Mn, Mo,  Ni, Se, Ag, Na, Tl,  V,  and Zn.  This study followed a



single-laboratory evaluation  that investigated the application



of Method  6010 to a variety  of  aqueous and solid-waste samples.



The different waste  matrices  studied in the single-laboratory



evaluation required the utilization  of several  different



digestion procedures.  In  contrast, this interlaboratory study



examined Method 6010  for the analysis of solid wastes that were



digested using a single digestion procedure.







     Since the digestion  of solid samples is necessary to apply



Method 6010  for the  analysis  of  wastes, a thorough study of

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Method 6010  must  also include  digestion  as  a variable.



Consequently, a parallel  study of Method  3050  (Acid  Digestion



of Sediments, Sludges,  and Soils) was included as an integral



part of the interlaboratory study.   The present study  was



designed  to determine the performance of Method  6010  both



independent of and together with  the Method  3050 digestion



procedure.







     Seven solid materials, representative of solid  wastes,



were selected as the  method evaluation materials.  Three  of the



materials  (river  sediment,  coal  fly  ash,  and estuarine



sediment) are Standard  Reference Materials  from  the National



Bureau of Standards, and one material  (the mine tailing) is an



EPA reference material.   The other  three solids  (a  contaminated



soil and two" industrial  sludges) were obtained  from the EPA.  A



detailed homogeneity  study was  performed by the  coordinating



laboratory  before the  solids  were  distributed to  the



participating laboratories.  The  results indicated that  the



solid samples were homogeneous.







     Sixteen grams of these homogeneous solids  were distributed



to the  laboratories to be digested by Method 3050,  both



unspiked and spiked.   The spiking solutions  provided to the



laboratories contained 19 of the 23  target elements.  They  were

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designed to be added  to  the  solids prior to digestion to bring
the concentrations  of  the  19 elements in the laboratories'
digests to minimum  levels  of  about 100 times the corresponding
"Estimated  Instrumental Detection Limits" given in Method  6010.
It was  not necessary to  spike Al,  Ca, Fe, and Mg  into  the
solids because of the high endogenous  concentrations  of  these
metals in the 7 solid  samples.   Having each laboratory spike
portions of the solid samples with the  spiking solutions  prior
to digestion assured  that  each  laboratory used equally spiked
aliquots of the solids.  This procedure eliminated the need to
create uniformly spiked solids for distribution.  The  resulting
digests were analyzed by Method 6010.

     In order to  remove  sample-preparation  variability from
measurement variability,  bulk digests of the  7 solid samples
were prepared by  the  coordinating laboratory for distribution
to the participating  laboratories.  These bulk digests were
spiked with the same  spiking  solutions that were used to spike
the solid samples.   Thus,  the  spiked bulk digests of  the  seven
solid samples were  very  similar in composition to the spiked
solids  digests that were prepared  by the  laboratories.
Therefore, data from  the Method 6010 analyses of these spiked
bulk digests could be compared to data from  the spiked  solids
in order to estimate  the variances due to  the digestion  and

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analysis" procedures.   In  order  to  test  the  effects  of high



levels of V and Mo on the determination  of the other analytes



by Method 6010, the  spiked bulk  digest from the fly ash solid



was also spiked to contain 0.1 percent of  these  interfering



elements.







     In addition  to the solid samples  and  the spiked bulk



digests, two QC solutions containing  the target elements were



provided to the participating laboratories for  analysis with



and without digestion. Because these  solutions were carefully



prepared  and verified by the coordinating  laboratory,  the



results could be used to estimate the  accuracy  of the Methods.



Other solutions were provided to the  participating laboratories



to insure high ICP-AES data quality.    These were  initial



calibration verification solutions  and an  interference check



solution.







     The  results of  this  collaborative  study yielded



quantitative information on  the  precision and accuracy  of



Method 6010, independently and together with Method 3050.  Data



obtained on sequential and simultaneous ICP-AES instruments  as



well as by atomic absorption spectroscopy  (AAS) were  compared



statistically, and the results are  reported.   The method  of

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standard additions (MSA) is a conditional requirement of Method
6010,  so  its effect on data quality was investigated.
                   RESULTS AND DISCUSSION

     This  mul t i 1 a bor a t or y  evaluation  of  Method 6010
demonstrates that  the method,  as  described,  is  capable  of
achieving excellent  accuracy and precision  for the
determination of the  23  elements in quality  control  (QC)
solutions.  These  QC  solutions contained  the  23  elements  at
concentrations of  approximately 100  times the  instrumental
detection limits,  and the solutions  were interference-free in
that  no interfering  elements were present at high
concentrations.  Accuracy for  the multilaboratory analyses of
the QC solutions (when the mean values are expressed  as  a
percentage of the  target values) varies from 95  percent to 104
percent  for the solutions analyzed without digestion and  varies
from  93  percent to  103  percent  (silver excluded)  for the
solutions digested before being analyzed.  Digestion of  the  QC
solution containing silver resulted in a mean silver value that
is only  53 percent of  the target value  whereas the  mean  silver
value is  100 percent of the  target value for  the  direct
analyses of this QC  solution.  The  percent  RSD's for the

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elements range  from 3.1 percent to 9.1 percent for the QC



solutions that were analyzed  by Method 6010 without digestion



and from  2.6 percent  to  13  percent (when silver is excluded)



for the QC solutions  that were analyzed after digestion by



Method 3050.  The  median percent RSD's for the 2 sets of QC



solutions are 6.5 and  6.7  percent,  respectively.   This



precision is considered  excellent for these  solutions.  Silver



with a percent RSD of 52 is the lone outlier in the QC  solution



set that  was digested before  analysis.







     The  interlaboratory precision for Method  6010, with



digestion eliminated as a  variable, was determined for the 23



elements  in the spiked bulk  digests of six representative  solid



complex matrices,  including river and estuarine sediments and



industrial sludges  (Table 1).   The analyte concentrations in



these spiked bulk digests  were about 100 times the instrumental



detection limits.  The median percent RSD's for the 6 sediments



across 23 elements range from 6.8 percent to 11 percent.  Thus,



the precision for  the measurement of the target elements in



these complex solutions is very good.







     The  seventh spiked  bulk digest, from coal fly  ash, was



spiked with very  high levels of molybdenum and vanadium  (0.1



percent).  The median percent RSD's for the determination of

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TABLE 1.   PERCENT RSD's FOR THE DETERMINATION OF THE 23 TARGET ELEMENTS
           IN THE SPIKED BULK DIGESTS


ELEMENTS
Al
Sb
AS
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Mo
Ni
Se
Ag
Tl
V
Zn
Ba
Na
K
MEDIAN
PERCENT
RSD
HAZARDOUS
WASTE 1

11
5.6
13
5.8
11
8.8
6.2
11
4.4
6.6
15
8.8
10
20
9.4
7.5
44
19
12
9.1
11
17
8.8

10

RIVER
SEDIMENT

19
52
11
5.8
6.6
9.4
5.5
14
4.3
8.3
7.2
8.1
13
33
8.9
13
23
13
58
6.7
10
38
7.4

10

FLY
ASH

16
73
83
57
5.7
5.6
36
21
9.7
8.8
22
15
14
19
8.1
16
17
22
7.5
7.6
8.7
49
4.2

16

ESTUARINE
SEDIMENT

1.9
8.7
22
4.8
7.6
5.3
7.6
6.8
6.0
6.0
4.7
9.4
11
28
5.4
6.2
46
29
7.3
15
6.4
4.7
4.8

6.8

INDUSTRIAL
SLUDGE

11
3.2
25
6.4
3.1
8.5
5.8
6.7
11
6.9
3.9
8.0
11
16
5.1
13
47
30
5.5
10
8.0
5.8
13

8.0

ELECTRO-
PLATING
SLUDGE
13
24
8.6
9.9
9.8
7.0
7.8
11
7.8
8.4
5.6
20
9.6
36
9.2
13
19
20
11
2.5
20
9.8
5.8

11

MINE
TAILING

7.6
4.4
5.3
8.5
12
7.9
39
15
12
8.4
8.0
10
5.5
21
12
19
27
29
18
16
11
7.9
7.9

11


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the 23 elements in this spiked digest  range from 4.2 percent to
83 percent with a median of 16  percent  (Table 1).  The  12
percent median RSD for fly ash  digests without added Mo and V
(Table 2) suggests  that  these  two elements  decreased  the
measurement precision.of many of the target elements.

     When  Method 6010  and  Method 3050  are applied  in
combination for the determination of the  23 elements  in  spiked
solids, the apparent measurement precision decreases  (Table 2)
when compared to the corresponding spiked  bulk digest.   The
median percent RSD's for the  7  solids  across  the 23 elements
range from 11-17 percent.  The spiked solid samples were  spiked
prior  to digestion to assure  that the  concentrations  of the
analytes  in the resulting digests were  approximately  100 times
greater than the instrumental detection  limits.  The accuracy
of the ICP Method 6010 can be  estimated  for  these complex
matrices by comparing  the average  concentrations of  the
elements  in the spiked bulk digests (as determined  by  Method
6010)  to the corresponding concentrations which were  determined
by AAS by one of  the participating  laboratories.  A  null
hypothesis approach that is  based  on  the mean and  on the
corresponding standard deviation  was used to determine  if the
ICP-AES and AAS values are significantly different  at the 95
percent confidence level.  The  results indicate that only two
                              8

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TABLE 2.   PERCENT RSD's FOR THE DETERMINATION OF THE 23 TARGET ELEMENTS
           IN THE SPIKED SOLIDS
HAZARDOUS
WASTE 1
ELEMENTS
Al
Sb
As
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Mo
Ni
Se
Ag
Tl
V
Zn
Ba
Na
K
MEDIAN
PERCENT
RSD
17
27
13
16
13
7.3
7.9
18
12
14
15
5.9
14
19
13
13
19
19
18
14
8.4
14
19

14'

RIVER
SEDIMENT
24
56
26
13
8.
9.
22
22
14
19
6.
8.
9.
31
20
9.
7.
28
19
12
9.
40
17

17




4
0




4
4
0


4
6



8





FLY
ASH
20
25
16
7.6
9.3
12
9.7
12
10
44
9.6
17
11
24
9.7
9.8
50
34
12
11
7.2
32
18

12

ESTOARINE
SEDIMENT
22
62
22
11
14
10
7.1
9.2
9.7
16
11
9.0
10
18
10
10
34
28
10
13
14
9.4
18

11

INDUSTRIAL
SLUDGE
14
28
20
18
19
12
18
18
19
18
20
16
16
18
20
15
30
18
18
20
16
20
22

18

ELECTRO-
PLATING
SLUDGE
18
40
20
7.0
18
14
12
13
9.4
14
19
10
18
43
15
18
27
43
39
8.2
30
15
5.7

18

MINE
TAILING
26
58
22
16
20
12
26
18
12
18
5.8
10
9.4
20
17
12
50
44
24
20
7.2
12
16

18


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out  of  184 elemental measurements  by  the two methods  are



significantly  different.   The  ICP-AES mean value was



statistically higher  than  the  AAS value  for Ca in the digests



of the Estuarine Sediment  and the Mine Tailing Waste.   In some



cases where the  ICP/AAS  ratios are very  different (less than



0.75 or  greater than 1.25),  the  standard deviations in  the  ICP



measurements are very high, and, therefore,  the differences in



the means  are not significant.   Overall, the agreement  between



ICP and AAS is excellent.







     The median percent RSD's  for the same 7 solids, unspiked,



range from 17-27 percent (Table  3).  This poorer precision when



compared  to the  spiked solids  results because over 50 percent



of the reported  concentration  values are  less than 100  times



the  average of  the instrumental detection limits.   In  other



words,  as the  concentrations approach the  instrumental



detection limits the  precision decreases as indicated by  the



higher percent RSD values.   Four elements among those  with  the



highest median percent RSD's are antimony, selenium, silver  and



arsenic.   For those elements that were present in the  digests



of the unspiked solids at concentrations 100 times greater than



the IDL's  (due  to their occurrence in high concentrations  in



the  unspiked solids), the precision is comparable to  the



precision  for the spiked solid samples.
                              10

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TABLE 3.  PERCENT RSD'S FOR THE DETERMINATION OF THE 23 TARGET ELEMENTS
          IN THE UNSPIKED SOLIDS

ELEMENTS
Al
Sb
As
Be
Cd
Ca
Cr
Co
Cu
Fe
Pb
Mg
Mn
Mo
Ni
Se
Ag
Tl
V
Zn
Ba
Na
K
MEDIAN
PERCENT
RSD
HAZARDOUS
WASTE 1

19
38
53
31
37
9.0
11
24
10
13
8.0
6.0
8.6
30
14
42
41
31
21
14
7.4
66
23

21

RIVER
SEDIMENT

32
78
48
27
17
13
19
60
9.4
24
12
11
17
42
25
61
43
30
72
12
11
52
34

27

FLY
ASH

19
—
32
27
57
10
28
23
16
52
33
20
24
20
34
—
47
—
15
20
4.3
34
20

23

ESTUARINE
SEDIMENT

23
—
18
35
52
11
22
12
17
10
37
10
10
58
21
30
1.4
—
17
8.6
14
9.1
17

17

INDUSTRIAL
SLUDGE

15
47
83
42
17
10
12
21
17
14
16
18
18
56
16
43
38
38
28
12
24
16
32

18

ELECTRO-
PLATING
SLUDGE
23
68
44
70
22
17
12
46
12
12
17
14
21
49
20
74
54
45
35
9.2
38
17
9.6

22

MINE
TAILING

17
57
28
41
59
8.6
90
30
20
18
17
9.2
11
26
40
77
60
120
47
20
8.8
13
24

26


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     The Method 6010 variance and the Method 3050 variance can



be calculated from the  data base resulting  from the analyses of



the spiked bulk digests  and the spiked solid samples (Table 4).



A statistical analysis  of the  data shows that in general, the



digestion procedure  and the  ICP-AES analytical procedure



contribute about equally  to the overall measurement uncertainty



or precision (variance)  for the determinations of the 23  target



elements in digests of  these 7 homogeneous  solids.







     The method  of  standard  additions was required for less



than 10 percent  of  the  total  analyses.   Results  by  ICP-AES



using  the method  of  standard additions were compared with



non-MSA data  for  the spiked bulk  digest samples.   The



comparison of  this limited data set (Table 5) indicates  that on



the average there  is  no consistent  improvement in  the data



quality when  the  method of  standard additions is used with



Method  6010 for the  analysis  of the  solid matrices that were



used in this study.







     A  comparison  between  data obtained on simultaneous and



sequential inductively  coupled plasma spectrometers indicated



that  the concentration  values were statistically



indistinguishable.
                              12

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TABLE 4.  ESTIMATED PERCENTAGE CONTRIBUTIONS OF METHOD 6010 ICP
 VARIANCE AND METHOD 3050 DIGESTION VARIANCE TO TOTAL VARIANCE
Elements
Al
Cd
Ca
Co
Cu
Fe
Pb
Mg
Mn
Mo
Ni
Se
Tl
Zn
Ba
K
Be
V
Sb
As
Cr
Na
Ag
6010 ICP
41
26
50
39
38
11
66
100
68
100
27
89
63
55
37
22
25
24
3
35
26
25
100
3050 Digestion
59
74
50
61
62
89
34
0
32
0
73
11
37
45
63
76
75
76
97
65
74
75
0
           Median:         46                 55
                                13

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           TABLE 5.   COMPARISON OF MSA AND NON-MSA RESULTS3
SPIKED BULK DIGESTS
NON-MSA

SAMPLE NAME
HAZARDOUS WASTE
HAZARDOUS WASTE
HAZARDOUS WASTE
RIVER SEDIMENT
FLY ASH
FLY ASH
FLY ASH
FLY ASH
FLY ASH
FLY ASH
ESTUARINE SEDIMENT
INDUSTRIAL SLUDGE
ELECTROPLATING SLUDGE
MINE TAILING

ELEMENT
Cd
Tl
Zn
Tl
Cd
Cr
Pb
Mn
Ni
Tl
Tl
Tl
Tl
Cd

N
5
5
5
7
5
5
4
4
3
4
5
5
3
5
MEAN

CONG. SD
894
4410
4310
3160
754
1480
4100
1910
1530
5530
3870
4470
4600
850
117
788
426
2210
422
885
634
233
154
3730
1290
872
740
69

N
3
3
3
3
3
3
4
3
4
3
3
3
4
3
MSA
MEAN

CONC. SD
940
4510
4560
5050
897
2390
6770
1750
1350
1950
3340
4620
5350
985
84
1130
250
675
219
1090
3300
304
500
2470
2850
2230
1120
112

%RATIO
95
98
95
63
84
62
61
109
113
284
116
97
86
86
SIG.
DIF.C
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
Only those elements that required the application of the MSA by three or
more laboratories are included as statistically significant.
Concentration for liquids in ug/L; concentration for solids in rag/kg.
Result of a null hypothesis approach used to indicate whether MSA and non-MSA
results are significantly different.
N - Number of cases.
% Ratio - non-MSA to MSA mean concentrations.
                                                                      (continued)

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TABLE 5.  (continued)

UNSPIKED SOLIDS
SAMPLE NAME ELEMENT
HAZARDOUS WASTE
HAZARDOUS WASTE
HAZARDOUS WASTE
HAZARDOUS WASTE (DUP.)
RIVER SEDIMENT
RIVER SEDIMENT
RIVER SEDIMENT
RIVER SEDIMENT
RIVER SEDIMENT (DUP.)
RIVER SEDIMENT (DUP.)
FLY ASH
MINE TAILING
MINE TAILING
MINE TAILING (DUP.)
MINE TAILING (DUP.)
MINE TAILING (DUP.)
MINE TAILING (DUP.)
ELECTROPLATING SLUDGE
ELECTROPLATING SLUDGE
ELECTROPLATING SLUDGE (DUP.)
ELECTROPLATING SLUDGE (DUP.)
INDUSTRIAL SLUDGE
Be
Cr
Co
Ni
Sb
Cd
Co
Ni
Cd
Ni
Be
Cd
Zn
Cd
Co
Ni
Zn
Cd
Mn
As
Mo
As
N
4
6
6
5
6
6
5
6
6
6
6
4
6
4
6
5
6
6
6
6
5
4
NON-MSA
MEAN
CONG. SD
0.8
95
8.0
17
325
11
21
44
10
39
3.0
2.3
372
2.4
7.3
21
365
113
226
33
14
11
0.1
8.4
2.4
1.3
266
2.5
16
20
1.6
13
0.8
1.6
44
1.6
2.5
5.6
43
24
31
20
11
6.6
N
3
3
3
4
3
3
4
3
3
3
3
3
3
3
3
4
3
3
3
3
3
3
MSA
MEAN
CONG.
0.7
111
9.1
13
169
11
21
27
10
38
2.6
1.9
340
1.5
8.8
21
345
96
254
41
21
26
SD
0.2
10
1.5
8.9
246
3.5
19
7.0
0.7
19
1.2
1.1
119
0.8
3.1
11
122
41
126
20
7.3
11
%RATIO
93
86
88
128
192
103
99
161
107
105
114
122
109
158
83
100
106
118
89
80
68
41
SIG.
DIF.C
NO
YES
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
NO
YES
                                         (Continued)

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TABLE 5. (concluded)

SPIKED SOLIDS
NON-MSA
MEAN .
SAMPLE NAME ELEMENT
HAZARDOUS WASTE
HAZARDOUS WASTE
HAZARDOUS WASTE
HAZARDOUS WASTE
HAZARDOUS WASTE (DUP.)
HAZARDOUS WASTE (DUP.)
HAZARDOUS WASTE (DUP.)
ESTUARINE SEDIMENT
ESTUARINE SEDIMENT
ESTUARINE SEDIMENT
ESTUARINE SEDIMENT
ESTUARINE SEDIMENT (DUP.)
MINE TAILING
MINE TAILING (DUP.)
ELECTROPLATING SLUDGE (DUP.)
Co
Pb
Mo
Ni
Co
Pb
Ni
Cd
MO
Ni
Tl
Ni
Ni
Ni
Tl
N
6
6
6
6
6
6
6
6
6
6
6
6
6
6
6
CONG. SD
45
340
39
57
48
390
61
46
37
65
180
63
64
63
160
8.2
104
20
10
4.8
29
3.5
4.7
19
6.7
65
6.9
7.9
6.9
46
N
3
3
3
3
3
3
3
3
3
3
3
3
3
3
3
MSA
MEAN
CONC.b
30
238
29
37
56
338
58
53
47
73
239
74
60
64
304


SD %RATIO
2.2
14
2.8
2.9
11
112
14
2.2
2.5
1.3
24
3.3
15
19
104
149
143
134
152
85
115
106
87
79
89
75
86
108
99
53
SIG.
DIF.C
YES
NO
NO
YES
NO
NO
NO
NO
NO
NO
NO
YES
NO
NO
YES

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                       RECOMMENDATIONS








     The experimental design  used in this multilaboratory study



has resulted  in  several  excellent sets of multidimensional



analytical data  that  deserve consideration beyond  the intended



scope of this  report.  Further analysis and interpretation of



this data base is suggested.







     The presence of high concentrations (0.1  percent) of added



vanadium and molybdenum in the fly ash spiked bulk digest could



account  for the  apparent decrease in the precision of Method



6010 for the determination of  many of the 23 target  elements in



this  matrix  compared to  the  6 other  solid  digests.   The



interfering effects in this matrix should be studied further.








     The poor precision, accuracy, and spike  recoveries for



silver  demonstrated in this  study, should .be  noted in  both



Method  3050 and  Method 6010. The possibility of precipitation



in the  nitric/hydrochloric acid digestion matrix as well as



phototransformation should be  discussed in Method 3050.
                             17

-------
     The poor  spike recovery of antimony, observed in this
study, should be noted in Method 3050.  In particular, the
possibility of the  formation of  oxide and  oxo-chloride
precipitates of antimony in the nitric/hydrochloric acid
digestion matrix should be discussed.

     The application of the method of standard  additions  (MSA),
a conditional requirement of  Method  6010,  affects the
economics, the turnaround time of analysis,  the practicality  of
the Method, as well  as the data quality.  Although this  report
indicates that, on  the average, MSA data were  not consistently
different  from  non-MSA data,  the  requirement for the
application of the MSA should be investigated further.

     When  soil-containing matrices  are  being analyzed by Method
6010,  the  authors  are  of  the  opinion that the method  of
standard additions  should  not be required for  those elements
that are endogenous to  soils  in  high concentrations.  The
high-concentration  endogenous elements  in soils include  Al,  Ca,
Fe,  Mg, K, and Na.
                             18

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Information box:








     The authors  are with the Environmental Research Center,



University of Nevada,  Las Vegas, Nevada  89119-9770.  Thomas A.



Hinners is with the EPA at  EMSL, Las Vegas, Nevada 89193-3478.








     The complete report,  entitled  "An  Interlaboratory Study of



Inductively Coupled Plasma  Atomic Emission Spectroscopy  Method



6010 and Digestion Method 3050," will be available only from:








     National Technical Information  Service



     5285 Port Royal Road



     Springfield,  Virginia   22161



     Telephone:  703-487-4650








     The EPA Technical Monitor under which the  work was done



was Thomas A. Hinners.  He  can  be contacted at:








     Environmental Monitoring Systems Laboratory



     U.S. Environmental Protection Agency



     P.O. Box 93478



     Las Vegas, Nevada  89193-3478



     Telephone:  702-798-2140
                               19

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